Resin compositions and uses thereof

ABSTRACT

The invention pertains to a resin composition comprising a polymer and a solvent, characterized in that the polymer is obtained by polymerizing the following monomers:  
     (a) an acrylate monomer;  
     (b) a tertiary carboxylic ester; and  
     (c) a monomer selected from the group consisting of a fluoro acrylate monomer, a silicone monomer, and a mixture thereof.  
     The resin composition of the invention can be formulated into a coating for a substrate to impart stain resistance to the coated surface.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a resin composition comprising apolymer and a solvent. The resin composition of the invention can beformulated into a coating for a substrate to impart a stain resistanceto the coated surface.

[0003] 2. Description of the Prior Art

[0004] In the past, a coating material for forming a protective layer ona substrate was normally required to be conveniently applied to thesurface of the substrate and adhered to the surface permanently so as toobtain an aesthetic appearance. A coating material had not been strictlyrequired to exhibit stain resistant properties. However, there arematerials existing in our living environment which will contaminate acoating layer, damage the appearance of the coated surface, deprive thecoated surface of protection properties, and shorten the duration timeof the coating.

[0005] It is conventional to apply an acrylic resin coating, an alkydresin coating, a novolak resin coating, an amino resin coating, or anepoxy resin coating to the surface of a substrate. Although the resincoatings may meet short-term requirements, due to the poor structuralmorphology, low surface hardness, and high surface energy of the resinsper se, the resin coatings would not be able to provide the coatedsurfaces with satisfactory stain resistant properties. Since coatingsthat satisfy consumers' needs should possess highly stain resistantproperties, in coating industry, there is a continuous need for acoating material exhibiting satisfactory stain resistant performance.

[0006] JP 6-345823 discloses a fluorine-containing copolymer resin whichmay provide good weathering resistance and water repellence after along-term outdoor exposure. The copolymer is obtained by polymerizing ahydroxy-containing acrylate monomer, a fluoroolefin monomer and aperfluorovinyl monomer. The resultant resin is cured by a non-yellowingisocyanate curing agent at room temperature to form a coating. Upon asix-month outdoor exposure, the coating still keeps the original surfacegloss and water repellence.

[0007] JP 7-026204 discloses a fluorine-containing polyurethane polymer.The polymer is prepared from the polymerization of a polyol which has anunsaturated group in the molecule and has an average molecular weight offrom 300 to 3,000 and perfluoro acrylic acid or a perfluorovinylmonomer. The resultant resin is cured by an isocyanate ester at roomtemperature to form a coating. Upon a 2000-hour exposure in an expeditedweathering tester, the coating retains more than 88% of the originalsurface gloss, higher than the 70% surface gloss of thefluoroolefin-vinyl ether polymer coating produced by Asahi GlassFluoropolymers Co., Ltd. The organic fluoro polymer coating of JP7-026204 is resistant to weathering, corrosion, and chemicals.

[0008] Although the above-mentioned prior art techniques may resolve theproblem associated with the staining of coatings resulted from somestaining materials, it is still necessary to seek for other coatingmaterials exhibiting stain resistance against other staining sources.

[0009] Moreover, there are prior art techniques that incorporate a longfluoro side-chain into a resin and provide the resin with —OH radicalsso as to impart reactivity to the product. However, in view of thedifference in the polarities of the monomers, there would exist phaseseparation in the resultant resins which would result in the breaks ofthe coating film and the reduction of the stain resistance of thecoating film.

DESCRIPTION OF THE INVENTION

[0010] The inventors of the application found that by utilizing a longside-chain fluoro segment or silicone segment, the surface tension ofthe resultant coating film can be reduced and the stain resistancethereof will be enhanced. In addition, the invention uses tertiarycarboxylates to impart compatibility to the resultant fluoro-containingcoating film. The present invention could effectively resolve theproblems associated with the deterioration of coating films and thereduction in stain resistance of the coating films encountered in theprior art. Moreover, the coating composition of the invention mayutilize any kind of curing agents and be useful for a variety ofsubstrate materials.

[0011] Accordingly, the present invention provides a resin compositioncomprising a polymer and a solvent, wherein said polymer is obtained bypolymerizing the following monomers:

[0012] (a) an acrylate monomer;

[0013] (b) a tertiary carboxylic ester; and

[0014] (c) a monomer selected from the group consisting of a fluoroacrylate monomer, a silicone monomer, and a mixture thereof.

[0015] The solvent which may be useful in the composition of the presentinvention is obvious to persons skilled in the art. Examples of thesolvent include a benzene compound, an ester, and a ketone, and amixture thereof. Non-limiting examples of the benzene solvent includebenzene, o-xylene, m-xylene, p-xylene, trimethylbenzene, and styrene,and a mixture thereof. Non-limiting examples of the ester solventinclude ethyl acetate, butyl acetate, diethyl carbonate, ethyl formate,methyl acetate, ethoxyethyl acetate, ethoxypropyl acetate, andmonomethyl ether propylene glycol ester, and a mixture thereof.Non-limiting examples of the ketone solvent include acetone, methylethyl ketone, and methyl isobutyl ketone, and a mixture thereof.

[0016] In the composition of the present invention, the solvent ispresent in an amount, based on the total weight of the composition, offrom 20 to 70 wt %, preferably from 30 to 60 wt %.

[0017] The acrylate monomer used to form the polymer of the inventionhas the following general formula:

[0018] wherein R¹ is halogen, H, CH₃, or C₂H₅; and R² is H, CH₃, C₂H₅,C₃H₇, C₄H₉, C₂H₄OH, C₃H₆OH, NH₂, C₁₀H₁₇, or the group of the followingformula:

[0019] Preferred acrylate monomers include acrylic acid, methacrylicacid, methyl acrylate, methyl 2-methyl-acrylate, butyl acrylate, butylmethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,2-hydroxypropyl methacrylate, or hexyl 2-ethylacrylate, and a mixturethereof. The amount of the acrylate monomer, based on the total weightof the monomers used, is in the range of from 20 to 80 wt %, preferablyfrom 30 to 70 wt %.

[0020] The tertiary carboxylic ester used to form the polymer of theinvention has the following general formula:

[0021] wherein R³, R⁴, and R⁵ independently represent a straight orbranched alkyl chain: C_(m)H_(2m+1), wherein m is an integer rangingfrom 1 to 15, and R⁶ is selected from the group consisting of

[0022] Preferred tertiary carboxylic esters include vinyl saturatedtertiary decanoate, vinyl saturated tertiary nonanoate, and epoxy propylsaturated tertiary decanoate and a mixture thereof. The amount of thetertiary carboxylic ester, based on the total weight of the monomersused, is in the range of from 5 to 50 wt %, preferably from 5 to 30 wt%.

[0023] The fluoro acrylate monomer used to form the polymer of theinvention has the following general formula:

R^(f)CH₂C₂O(O)CC(R)═CH₂

[0024] wherein R^(f) is a straight or branched perfluoroalkyl chain:C_(n)F_(2n+1), wherein n is an integer ranging from 2 to 20, and R is H,CH₃, C₂H₅, or C₃H₇.

[0025] Preferred fluoro acrylate monomers include a fluoroalkylmethacrylate or a mixture thereof. More preferably, the fluoro acrylatemonomers are of the above formula in which n ranges from 6 to 14.According to the present invention, the amount of the fluoro acrylatemonomer, based on the total weight of the monomers used, is in the rangefrom 1 to 40 wt %, preferably from 1 to 20 wt %.

[0026] The silicone monomer used to form the polymer of the presentinvention has the following general formula:

[0027] wherein R⁷ and R⁸ independently are H, CH₃, CH₂═CH, NH₂,NH₂—C₃H₆, OH—C₂H₄₀C₃H₆, CH═CCH₃—COOH, CH═CH—COOH, or

[0028] wherein n=10 to 250.

[0029] When used in the present invention, the amount of the siliconemonomer, based on the total weight of the monomers used, is in the rangeof from 1 to 40 wt %, preferably from 1 to 20 wt %.

[0030] The polymer of the present invention may optionally comprise avinyl monomer of the following general formula:

[0031] wherein R is selected from the group consisting of:

[0032] Preferred vinyl monomers include styrene, vinyl ethyl ether,cyclohexyl vinyl ether, 4-hydroxybutyl vinyl ether, n-butyl vinyl ether,isobutyl vinyl ether, n-propyl vinyl ether, and isopropyl vinyl ether,and a mixture thereof. If present, the amount of the vinyl monomer,based on the total weight of the monomers used, is in the range of from5 to 40 wt %, preferably from 5 to 25 wt %.

[0033] The polymer of the invention can be prepared by any methods wellknown to persons skilled in the art. For example, the various monomersused in the polymerization for preparing the polymer of the presentinvention may be mixed with a suitable solvent and an initiator, andpolymerized at a suitable temperature and reaction time to form thepolymer of the invention.

[0034] Optionally, the composition of the invention may be formulatedinto a coating by incorporating a conventional additive, such as acuring agent, well known to persons skilled in the art, and be coated onthe surfaces of any suitable substrates, such as a metal, an alloy, acomputer case, wooden material, plastic material, leather, or stonematerial, so as to impart stain resistance to the coated surfaces.Suitable curing agents include, but not limited to, melamine, methylatedmelamine, or isocyanate ester.

[0035] The present invention will be further described in the followingexamples. However, the examples will not make any limitations to thescope of the invention. Any modifications or alterations on theinvention that can be easily accomplished by persons skilled in the artare encompassed in the disclosure of the specification and theaccompanying claims.

EXAMPLES

[0036] Definition:

[0037] AA: acrylic acid

[0038] MAA: methacrylic acid

[0039] MMA: methyl methacrylate

[0040] IBMA: isobornyl methacrylate

[0041] BA: butyl acrylate

[0042] BAc: butyl acetate

[0043] n-BMA: n-butyl methacrylate

[0044] 2-HPMA: 2-hydroxypropyl methacrylate

[0045] FAMA: 2-(perfluoroalkyl)ethyl acrylate and a mixture thereof

[0046] AS: silicone methyl methacrylate

[0047] GETCA: neodecanoic acid glycidyl ester

[0048] PMA: propylene glycol monomethyl acetate

[0049] TBPB: t-butyl perbenzoate

Example 1-7

[0050] Resin compositions are prepared from the monomers and solvent atdifferent ratios as shown in the following Table 1: TABLE 1 Example no.1 2 3 4 5 6 7 Monomers/ AA 13.4 10.5 10.5 10.5 13.4 10.5 10.5 amounts(g) MAA 0.6 0.6 0.6 0.6 0.6 0.6 0.6 MMA 39.6 21.8 14.5 43.6 23.8 39.639.6 IBMA — 21.8 29.0 — — — — BA 17.1 — — — 39.6 14.9 14.9 n-BMA — 10.510.5 10.5 — — — HPMA 13.2 31.5 31.5 31.5 6.6 28.6 28.6 FAMA 7.0 3.6 3.63.0 7.0 7.0 — AS — 7.0 7.0 7.0 — — — GETCA 46.6 18.6 18.6 18.6 46.6 36.323.3 Solvent (xylene) (g) 88 111 105 111 88 88 88 Addition of PMA (g)17.6 17.6 17.6 17.6 17.6 17.6 17.6 Initiator (g) TBPB 0.5 3.0 3.0 3.60.5 0.5 0.5 Reaction temperature 130° C. 130° C. 130° C. 130° C. 130° C.130° C. 130° C. Time (hour) 8 8 8 8 8 8 8 Solids content (wt %) 56.949.1 49.8 51.5 55.6 56.4 54

[0051] Stain Resistance Test for Resin Compositions

[0052] The formulations for stain resistance test, as shown in followingtable, are prepared from the compositions shown in Table 1. The resultsof the test are shown in Table 2 below. Paint Formula Resin composition  10 g Curing agent (cymel 303^(a)) or N-3390^(b)))  1.4 g/2.1 g BAc 5-7 g p-Methyl benzene sulfonic acid 0.01 g

[0053] Substrate: Tinplate

[0054] Curing:

[0055] High temperature, cymel 303: 150° C.×30 min

[0056] Low temperature, N-3390: 60° C.×30 min and 3 days at roomtemperature TABLE 2 Example Number High temperature Low temperaturecuring curing Staining Source 1 5 6 7 2 3 4 7 Stained by lipstick(Shiseido), 3 3 3 3 3 3 3 3 duration time (hour) Cleanness level afterbeing 1 2 1 5 2 2 2 5 wiped by tissue paper Stained by black marker pen,60 60 60 60 60 60 60 60 duration time (minute) Cleanness level afterbeing 1 2 2 5 2 2 2 5 wiped by tissue paper Stained by coffee, durationtime 60 60 60 60 60 60 60 60 (minute) Cleanness level after being wiped1 1 1 4 1 1 1 4 by tissue paper Stained by No. 30 Motor Oil 3 3 3 3 3 33 3 (Chinese Petroleum Corporation), duration time (hour) Cleannesslevel after being wiped 1 2 1 4 2 2 2 4 by tissue paper Stained bygolden-paint brush, 60 60 60 60 60 60 60 60 duration time (minute)Cleanness level after being wiped 2 2 2 5 2 2 2 5 by tissue paperStained by black crayon, duration 3 3 3 3 3 3 3 3 time (hour) Cleannesslevel after being wiped 1 2 1 5 2 2 1 5 by tissue paper Stained by 5%carbon black, 3 3 3 3 3 3 3 3 duration time (hour) Cleanness level afterbeing wiped 1 2 2 5 2 2 2 5 by tissue paper

[0057] According to the results shown in Table 2, the polymers obtainedfrom the monomers comprising a fluoroacrylate monomer or siliconemonomer exhibit excellent stain resistance.

What is claimed is:
 1. A resin composition comprising a polymer and asolvent, characterized in that said polymer is obtained by polymerizingthe following monomers: (a) an acrylate monomer; (b) a tertiarycarboxylic ester; and (c) a monomer selected from the group consistingof a fluoro acrylate monomer, a silicone monomer, and a mixture thereof.2. The composition of claim 1 wherein said solvent is a benzenecompound, an ester, or a ketone, or a mixture thereof.
 3. Thecomposition of claim 2 wherein said benzene compound is selected frombenzene, o-xylene, m-xylene, p-xylene, trimethylbenzene, and styrene,and a mixture thereof.
 4. The composition of claim 2 wherein said esteris selected from the group consisting of ethyl acetate, butyl acetate,diethyl carbonate, ethyl formate, methyl acetate, ethoxyethyl acetate,ethoxypropyl acetate, and monomethyl ether propylene glycol ester, and amixture thereof.
 5. The composition of claim 2 wherein said ketone isselected from the group consisting of acetone, methyl ethyl ketone, andmethyl isobutyl ketone, and a mixture thereof.
 6. The composition ofclaim 1 wherein

wherein R¹ is halogen, H, CH₃, or C₂H₅; and R² is H, CH₃, C₂H₅, C₃H₇,C₄H₉, C₂H₄OH, C₃H₆OH, NH₂, C₁₀H₁₇, or the group of the followingformula:


7. The composition of claim 6 wherein said acrylate monomer is selectedfrom the group consisting of acrylic acid, methacrylic acid, methylacrylate, methyl 2-methyl-acrylate, butyl acrylate, butyl methacrylate,2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropylmethacrylate, and hexyl 2-ethylacrylate, and a mixture thereof.
 8. Thecomposition of claim 1 wherein said tertiary carboxylic ester has thefollowing general formula:

wherein R³, R⁴, and R⁵ independently represent a straight or branchedalkyl chain: C_(m)H_(2m+1), wherein m is an integer ranging from 1 to15, and R⁶ is selected from the group consisting of


9. The composition of claim 8 wherein said tertiary carboxylic ester isselected from the group consisting of vinyl saturated tertiarydecanoate, vinyl saturated tertiary nonanoate, and epoxy propylsaturated tertiary decanoate, and a mixture thereof.
 10. The compositionof claim 1 wherein said fluoro acrylate monomer has the followinggeneral formula: R^(f)CH₂CH₂O(O)CC(R)═CH₂ wherein R^(f) is a straight orbranched perfluoroalkyl chain: C_(n)F_(2n+1), wherein n is an integerranging from 2 to 20, and R is H, CH₃, C₂H₅, or C₃H₇.
 11. Thecomposition of claim 10 wherein said fluoro acrylate monomer is afluoroalkyl methacrylate or a mixture thereof.
 12. The composition ofclaim 1 wherein said silicone monomer has the following general formula:

wherein R⁷ and R⁸ independently are H, CH₃, CH₂═CH, NH₂, NH₂—C₃H₆,OH—C₂H₄OC₃H₆, CH═CCH₃—COOH, CH═CH—COOH, or

wherein n=10 to
 250. 13. The composition of claim 1 further comprisingone or more vinyl monomers.
 14. The composition of claim 13 wherein saidvinyl monomer has the following general formula:

wherein R is selected from the group consisting of:


15. The composition of claim 13 wherein said vinyl monomer is selectedfrom the group consisting of styrene, vinyl ethyl ether, cyclohexylvinyl ether, 4-hydroxybutyl vinyl ether, n-butyl vinyl ether, isobutylvinyl ether, n-propyl vinyl ether, and isopropyl vinyl ether, and amixture thereof.
 16. The composition of claim 1 wherein said solvent ispresent in an amount, based on the total weight of the composition, offrom 20 to 70 wt %.
 17. The composition of claim 1 wherein said acrylatemonomer is present in an amount, based on the total weight of themonomers used, of from 20 to 80 wt %.
 18. The composition of claim 1wherein said tertiary carboxylic ester is present in an amount, based onthe total weight of the monomers used, of from 5 to 50 wt %.
 19. Thecomposition of claim 1 wherein said fluoro acrylate monomer is presentin an amount, based on the total amount of the monomers used, of from 1to 40 wt %.
 20. The composition of claim 1 wherein said silicone monomeris present in an amount, based on the total weight of the monomers used,of from 1 to 40 wt %.
 21. The composition of claim 13 wherein said vinylmonomer is present in an amount, based on the total weight of themonomers used, of from 5 to 40 wt %.
 22. A coating for the surface of asubstrate comprising the resin composition of claim
 1. 23. A method ofcoating the surface of a substrate comprising applying the resincomposition of claim 1 to the surface of the substrate.
 24. The methodof claim 29 wherein said substrate is a metal, an alloy, a computercase, a wooden article, plastic material, leather, or stone material.